苝酰亚胺
苝酰亚胺分子的制备
苝酰亚胺分子的制备
苯酰亚胺是一种重要的有机化合物，它可以通过多种方法进行
制备。
以下是其中一种常见的制备方法：
首先，你需要将苯甲醛和氨水混合，在室温下搅拌。
这会导致
苯甲醛与氨水发生反应，生成苯酰亚胺。
这个反应可以用下面的方
程式表示：
C6H5CHO + NH3 + H2O → C6H5C(O)NH2 + H2O.
在这个反应中，苯甲醛中的羰基和氨水中的氨基结合，生成了
苯酰亚胺。
需要注意的是，这个反应通常需要在较低的温度下进行，并且需要搅拌以保证反应充分进行。
除了上述方法，苯酰亚胺还可以通过其他途径进行制备，比如
使用苯甲酸和氨基化合物进行反应，或者利用其他酰胺化合物进行
反应等等。
这些方法都有各自的优缺点，可以根据具体情况选择合
适的方法进行制备。
总的来说，苯酰亚胺是一种重要的有机化合物，其制备方法多
种多样，可以根据实际需求选择合适的方法进行制备。
希望以上信息能够对你有所帮助。
乙酸介质中构筑苝酰亚胺染料长纳米线
乙 酸 介 质 中构 筑 茈 酰 亚 胺 染 料 长 纳 米 线
曹亚锋 ，解波雨 ，孙景志
（ 江大学高分子科学与工程学系 ， 浙 教育部高分子合成与功能构造重点实验室 ，杭州 ３０ ２ ） １０７ 摘要 合成 ＿一种带酰胺基的＿ 酰亚胺 ．紫外一 － ｒ 茈 可见光谱表明 ， 该化合物在乙酸和体 积分数大于 ４ ％ 的乙酸 ０
变过程．
关键词
纳 米 线 ； 酰亚 胺 ；分 子排 列 茈 ０ ４ ６３ 文献标识码 Ａ 文章 编 号 ０５ － ９ （０７ １—９４０ ２ １０ ０ ２ ０ ）０ １４ － ７ ４
中 图 分 类号
有 机半 导体在 电致发 光 与显示 器件 、 阳能 电池 和薄 膜 晶体 管 等领 域 的应 用 已 引起 了广 泛关 注 ， 太
仪上测定； 样品的微观形态分别在 Ｊ Ｏ Ｍ ５０型扫描 电子显微镜和 ＪＭ ０Ｃ Ｅ ＬＪ ５ １ Ｓ Ｅ ２０ Ｘ型透射 电子显微镜
上进行 观察 ．Biblioteka １２ 实验过 程 ．茈 酰亚胺 衍生 物 １的合成路 线见 Ｓ ｈｍｅ１ 实验 过程参 见文 献 ［ ５ ． ｃｅ ， ４， ］
核磁共 振 氢谱 、 外吸 收 光谱 、 外一 见 （ Ｖ Ｖｓ 吸 收 光谱 和 元素 分 析分 别 在 Ｍｅｃｒ ｌ ０ 红 紫 可 ｕ — ｉ） ｒ ｙｐｕ ３０ ｕ ｓ
型核磁 共振 波谱 仪 、Ｂｕ ｅ Ｉ Ｆ Ｉ ｒｋ ｒＶ型 Ｔ Ｒ分 析 仪 、 Ｅ Ｌ ｍ ｄ ０紫外一 见光谱 仪和 Ｐ ４ Ｃ型元 素分析 Ｉ Ｐ ａ ｂ ａ２ 可 Ｅ２ ０
产 物为红 褐色 固体 ， 收率 约为 ３．％ ． Ｈ Ｎ ８ １ ＭＲ（ 代氯 仿／ 代三 氟 乙酸 ） ６ ８７ ８８ （ 环 氘 氘 ， ： ．７～ ．０ 茈
苝酰亚胺自由基
苝酰亚胺自由基苝酰亚胺自由基是有机化学中的一种重要的中间体，具有广泛的应用价值。
本文将从苝酰亚胺自由基的定义、合成方法、反应特点以及应用领域等方面进行介绍。
苝酰亚胺自由基是指分子中含有苝酰亚胺基团（R-C=NR'）的自由基。
它的结构中有一个未成对电子，使其具有较高的反应活性。
苝酰亚胺自由基可以通过多种途径合成，其中最常用的方法是通过氧化反应获得。
例如，苯基苝酰胺可以通过过氧化苯基苝酰胺的热解来得到苝酰亚胺自由基。
苝酰亚胺自由基具有很强的反应活性，可以参与多种有机反应。
首先，它可以与另一个自由基发生反应，形成新的化学键。
这种反应被广泛应用于有机合成中，例如在氢转移反应中，苝酰亚胺自由基可以与醇类反应，形成醛或酮。
此外，苝酰亚胺自由基还可以参与自由基聚合反应，如自由基聚合聚合物的合成。
苝酰亚胺自由基还具有其他一些特殊的反应特点。
例如，它可以参与自由基加成反应，与烯烃或炔烃反应，形成新的C-C键。
此外，苝酰亚胺自由基还可以参与氧化反应，与氧气或氧化剂反应，生成相应的氧化产物。
苝酰亚胺自由基在有机合成领域具有广泛的应用价值。
首先，由于其反应活性高，它可以作为反应介质或催化剂参与多种重要的有机转化反应。
其次，苝酰亚胺自由基还可以用于有机合成中的碳-碳键构建。
此外，苝酰亚胺自由基还可以用于有机电化学反应、光化学反应以及自由基聚合反应等领域。
苝酰亚胺自由基是一种重要的有机中间体，具有广泛的应用价值。
它的合成方法多样，反应特点独特，可以参与多种有机反应。
在有机合成领域，苝酰亚胺自由基被广泛应用于催化剂、反应介质以及碳-碳键构建等方面。
随着有机化学领域的不断发展，相信苝酰亚胺自由基将发挥更加重要的作用，为有机化学合成提供更多的可能性。
新型苝酰亚胺衍生物的合成及其光学性能_杜斌
到限制。 为了改善 Ⅰ 的溶解度， 必须对其进行修 饰。针对 Ⅰ 的修饰主要集中于两个位置： 一是在
*
0326 收稿日期： 2012基金项目： 国家重点基础研究发展计划（ 973 ） 资助项目（ 2011CB706902 ） 作者简介： 杜斌（ 1987 － ） ， 男， 汉族， 山东济宁人， 硕士研究生， 主要从事军事化学与烟火技术的研究。 mail： fhyjy404@ 163． com 通信联系人： 余建华， 研究员， 博士生导师，E-
1 Vis 和荧光光谱研究了他们的光学性质 。 结构经 H NMR 和 MS 表征。用 UV-
关
键
词： 苝四酸二酐； 苝酰亚胺； 合成； 光学性质 文献标识码： A 1511 （ 2012 ） 04042104 文章编号： 1005-
中图分类号： O625
Synthesis and Optical Properties of Novel Perylene Diimide Derivatives
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苝酰亚胺
Liquid Crystalline Perylene Diimide Outperforming Nonliquid Crystalline Counterpart:Higher Power Conversion Efficiencies(PCEs) in Bulk Heterojunction(BHJ)Cells and Higher Electron Mobility in Space Charge Limited Current(SCLC)DevicesYoudi Zhang,†Helin Wang,†Yi Xiao,*,†Ligang Wang,‡Dequan Shi,‡and Chuanhui Cheng*,‡†State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian116024,People’s Republic of China‡School of Physical and Optoelectronic Engineering,Dalian University of Technology,Dalian116024,People’s Republic of China *Supporting Informationoptimized efficiency of0.94%.By contrast,the devices based on PDI-1,afficiency of0.22%.Atomic force microscopy(AFM)images confirmordered morphology.In space charge limited current(SCLC)deviceselectron mobility of2.85×10−4cm2/(V s)(at0.3MV/cm)which issame conditions for thermal annealing at120°C.semiconductor,perylene diimides,liquid crystalline,space charge limited current1.INTRODUCTIONIn recent years,liquid crystalline(LC)semiconductors have received considerable attention in thefields of organicelectronics.1−4Not only because they are readily dissolvable,butalso because they self-assemble into highly ordered morphology5 to effectively eliminate the structural and electronic defects.6,7LCmaterials are highly desirable for solution-processable devices.8It isnot surprising that some space charge limited current(SCLC) devices and organicfield-effect transistors(OFET)devices basedon LC semiconductors have shown very high charge mobility.9−13 However,in thefield of bulk heterojunction(BHJ)organic solar cells,the applicability of LC materials have not been well-recognized.14Actually,amorphous fullerenes derivatives,e.g.,PCBM,firmly occupy the dominant status as electron acceptors in BHJ cells,although have poor absorption in solar spectrum. Generally speaking,there is still a wide gap between non-fullerene organic acceptors and fullerenes in terms of BHJ efficiency.Among all the reported nonfullerene acceptors,one representative class is perylene diimides(PDIs),which have very strong absorption in the visible region and exhibit high electron mobility.However,because of their large,rigid,and planar conjugation cores,the seriousπ−πstacking and poor solubility of the PDIs and their analogues are problematic for BHJ cells;they tend to aggregate excessively to form islets,which not only damages the morphology of the BHJ active films but also generates carrier traps.A variety of strategies have been put forward to reduce the extent ofπ−πstacking,improve solubility,and control the aggregation state.15These working concepts include the introduction of swallow tail-type long, branchy,andflexible alkyl side chains onto the two imide sites,16−18copolymerization of PDI and other conjugated monomer on the perylene bay sites,19direct connection of two PDI segments on the imide site to form nonplanar and nonconjugate dimers,20and combination of PDI and donor on the imide site to form co-oligomers,21etc.Herein,we propose the utilization of liquid crystalline PDI derivatives,e.g.,LC-1,as a new means parallel to the above-mentioned ones helping to improve the applicability of PDIs in BHJ cells.In this work,LC-1,which is a structurely simple PDI derivative acting as the model of our strategy,has been adopted as the acceptor in the fabrication of BHJ cells’active layers with P3HT as the donor.Devices based on LC-1exhibit remarkably higher conversion efficiency than the nonliquid crystalline counterpart PDI-1.15To better understand the reason whyReceived:August9,2013Accepted:October15,2013Published:October15,2013LC-1is in favor of BHJ solar cells,its LC properities have been thoroughly characterized by di fferential scanning calorimetry (DSC),polarization optical microscopy (POM),and X-ray di ffraction (XRD);In addition,in spin-coated SCLC devices,LC-1’s intrinsic electron mobility is much higher than that of PDI-1.2.RESULTS AND DISCUSSION2.1.Fundamental Characteristics of LC-1Material.LC-1molecule was designed and synthesized according to a previous procedure,22as shown in Scheme 1.Solubility of LC-1was 40mg/mL in the common organic solution, e.g.,dichloromethane,chloroform,chlorobenzene,and dichloro-benzene,and it was very important for applied in BHJ solar cells.IN addition,the absorption spectra of LC-1do not have to change for modi fication of PDI N-terminal chains at 527nm in the solution and at 495nm in the film (see Figure 1).Thethermogravimetric analysis (TGA)curve showed the enhanced thermal stability for LC-1with a decomposition onset temperature (T d )of ∼333.7°C (see Figure 2).2.2.Photovoltaic Device Performance.In the compar-ison investigation on BHJ devices using liquid crystalline LC-1and n PDI-1,respectively,as acceptor materials,cells based on LC-1exhibited remarkably superior performances.For the device with P3HT:LC-1as an photovoltaic active layer,the optimum power conversion e fficiency (PCE)was 0.94%,which is ∼4times that of a device based on the P3HT:PDI-1(maximum PCE of 0.22%).These data supported our hypothesis that liquid crystalline acceptor materials are more advantageous in BHJ solar cells.Interestingly,there exists the regularity in the high dependence of devices ’s performances on the annealing temperature,which is related to the broad temperature range of LC-1’s liquid crystalline phase.Keeping the P3HT:LC-1weight ratio fixed at 1:2in the active layer,and setting a series annealing temperature (50,80,100,120,150,and 165°C),we tested the J −V curves of a group of BHJ devices (100mW cm −2AM 1.5G),as recorded in Figure 3,and we summarized the corresponding data in Table 1.Particularly,the correlation between annealing temperature and PCE and the correlation between annealing temperature and short-circuit current (J SC )had been clearly demonstrated in Figure 4.With the increase in annealing temperature from 50°C to 120°C,the continuous and obvious enhancements in device parameters including J SC ,open-circuit voltage (V OC ),and fill factor (FF)were found.The increased J SC may result from a reorientation and enhanced ordering of the LC-1during annealing,which would facilitate charge transport.However,at >120°C,further increases in the annealing temperature induced a decrease in device performance.Thus,using thermal annealing at 120°C resulted in the best data:PCE =0.94%,V OC =0.41V,J SC =5.42mA cm −2,and FF =0.42.In the control experiment,the BHJ device unannealed at 25°C only showed a much lower PCE of 0.23%,which is only a quarter of the optimum e fficiency.When we changed the P3HT:LC-1blended ratio into 1:1,the similar regularity on the e ffects of annealing temperature toScheme 1.Synthetic Routes of the Investigated LC-1MoleculeFigure 1.Normalized absorption spectra of (■)LC-1chloroform solution (1×10−5),(○)LC-1film,and (●)P3HT:LC-1blended film.Figure 2.TGA thermograms of liquid crystalline molecule LC-1measured under nitrogen flow (50mL min −1)at a heating rate of 10°C min −1.Figure 3.Current −voltage (J −V )curves of photovoltaic devices using P3HT:LC-1as active layers at temperatures of 25and 120°C and weight ratios of 1:1and 1:2,respectively.The curves correspond to the curve of P3HT:LC-1using (□)a weight ratio of 1:1at 25°C,(■)a weight ratio of 1:1at 120°C,(○)a weight ratio of 1:2at 25°C,and (●)a weight ratio of 1:2at 120°C.device data had also been observed;Again,the best performance (PCE =0.74%,V OC =0.38V,J SC =5.03mA cm −2,and FF of 0.39)was obtained under the condition of thermal annealing at 120°C.However,in the BHJ devices using the nonliquid crystalline PDI-1as the acceptor,thermal annealing did not seem to be as bene ficial as it did to LC-1.After annealing at 120°C,a device of P3HT:PDI-1(1:1)showed a J SC value of 1.6mA cm −2,V OC =0.34V,FF =0.40,and an e fficiency of 0.22%.These data were much lower than those obtained from the P3HT:LC-1device annealing at 120°C,but were similar to those of the unannealed P3HT:LC-1device.The above facts indicated that the improvement induced by thermal annealing was more related to LC-1’s liquid crystalline feature than to the perylene diimide conjugation core.To better understand the e ffects of the P3HT:LC-1weight ratio to photovoltaic performances,the comparisons of di fferent parameters (e.g.,external quantum e fficiencies (EQE)and internal quantum e fficiencies (IQE))were carried out.As shown in Figure 5A,the highest EQE (∼17%)was obtained for the blends of 1:2at 490nm,while for P3HT:LC-1(1:1)devices,the highest EQE value is just ∼13%at 485nm,the tested result implied that the increased proportion of LC-1molecule produced more photocurrent in the blended films and also veri fied the improved J SC observed in LC-1devices,which showed higher EQE values (peak EQE =17%)over the entire range of the active layer absorption from 350nm to 700nm,a signi ficant portion of that photocurrent is due to absorption by the acceptor phase,followed by hole transfer to the donor.As shown in Figure 5B,the IQE tests also suggested that much more charge carriers were generated for P3HT:LC-1(1:2)(∼22%)under sunlight,compared with that of the doping ratio of 1:1(∼16%).2.3.Atomic Force Microscopy Images.Atomic force microscopy (AFM)images revealed that the active layer morphology of P3HT:LC-1were greatly in fluenced by their weight ratios and the thermal annealing.As shown in Figure 6,a P3HT:LC-1ratio of 1:2produced much smoother morphology than ratio of 1:1;Also,the morphology after thermal annealing at 120°C was much smoother than that unannealed at 25°C.The root-mean-square (RMS)surface roughness values could be the indicators for the quality of films:the smaller the RMS surface roughness,the better the film morphology.On one hand,the smallest RMS surface roughness of 4.67nm for a doping ratio of 1:2under the thermal annealing at 120°C had been determined;this value was smaller than 5.50nm,which corresponds to the film without annealing.On the other hand,for the unannealed film with a doping ratio of 1:1,the RMS surface roughness value was 7.61nm,but after annealing at 120°C,the value decreased toTable 1.Performance of the Devices with Di fferent Weight Ratios and Thermal Annealing Conditions of P3HT:LC-1from o -Dichlorobenzene Solution Used for Spin Coatingtemperature [°C]PCE [%]J SC [mA cm −2]V OC [V]FF P3HT:LC-1Weight Ratio =1:1250.16 1.770.350.26500.43 3.580.360.33800.55 4.250.360.361000.65 4.330.400.381200.74 5.030.380.391500.67 4.310.410.381650.50 3.200.390.40P3HT:LC-1Weight Ratio =1:2250.23 1.880.360.34500.64 4.160.380.40800.71 4.670.370.411000.86 4.890.400.441200.94 5.420.410.421500.77 4.650.440.38P3HT:PDI-1Weight Ratio =1:1a1650.61 4.220.390.371200.22 1.600.340.40aThe mixing solution of P3HT:PDI-1was used as an organicphotovoltaic activelayer.Figure 4.Relationship chart of PCE and J SC versus temperature to P3HT:LC-1at di fferent temperatures and weightratios.Figure 5.(A)External quantum e fficiencies (EQE)and (B)internal quantum e fficiencies (IQE)of P3HT:LC-1at di fferent weight ratios.6.40nm.The decrease in the roughness of the blend films after annealing was due to the fact that the LC-1molecules were self-organized into ordered structures at 120°C within the liquid crystalline phase.The phenomenon that the increase in the proportion of LC-1in the blended film can improve morphology should also be ascribed to liquid crystalline characteristics.Because of the nonliquid crystalline feature of PDI-1,the morphology of the P3HT:PDI-1films would not be improved by the thermal annealing;the RMS surface roughness was high,up to 9.29nm,even after annealing at 120°C.Since the smooth morphology leaded to an e fficient charge separation,higher J SC and PCE for BHJ PV devices based on the thermally annealed blend films of P3HT:LC-1than those of P3HT:PDI-1can be partially explained.2.4.Charge Mobility.Charge mobility within an active layer film is another critical factor for BHJ cells.Since we had already found that,in P3HT:LC-1BHJ devices,thermal annealing greatly improved the PCE,for the sake of deeper interpretation of such e ffect,it would be useful to evaluate LC-1’s electron mobility at di fferent annealing temperature.Hence,we adopted the space charge limited current (SCLC)method,12,23−26which is suitable for determining organic semiconductors ’intrinsic carrier mobility under steady-state current.Consistent with the former P3HT:LC-1bulk hetero-junction solar cells device structure,the SCLC devices ’structure was designed to be ITO/ZnO (∼30nm)/LC-1(∼250nm)/LiF (1.5nm)/Al (100nm).J −V curves of the SCLC devices with spin-coated LC-1as the active layer annealed at di fferent temperatures were recorded (Figure 7),and the correspondingparameters have been collected in Table 2.The SCLC in this case of mobility,depending on the field,can be approximated by the following formula:27,28εεμγ=J E LE 98exp (0.89)020where E is the electric field across the sample;εand ε0are the relative dielectric constant and the permittivity of the free space,respectively;and L is the thickness of the organic layer,with μ0the zero-field mobility and γdescribing the field activation of the mobility.With the increase in annealing temperature,the electron mobility of LC-1first increased sharply,e.g.,from 4.90×10−6cm 2/(V s)at 25°C to 1.72×10−5cm 2/(V s)(at 0.3MV/cm)at 50°C;such a tendency of increase ceased at 120°C,where the electron mobility achieved the highest value,2.85×10−4cm 2/(V s),which is 50times higher than that of the unannealed device (25°C);Then,further temperature elevation would result in an apparent decrease in electron mobility,e.g.,to 2.93×10−5cm 2/(V s)at 150°C.Amazingly,such a correlation between the electron mobility of LC-1and annealing temperature exhibited the same regularity as that of the PCE of P3HT:LC-1BHJ solar cells.Hence,the best PCE of BHJ solar cells at 120°C can be reasoned by the highest electron mobility of LC-1at this temperature.29,30The SCLC device using the nonliquid crystalline PDI-1had also been tested.However,even if PDI-1film had undergone the thermal annealing at 120°C,the SCLC electron mobility was determined to be 5.83×10−5cm 2/(V s),which is only one quarter of that of LC-1.This fact could be used to explain why BHJ cells using LC-1as an acceptor outperformed those using PDI-1.In BHJ organic solar cells,the balanced charge carrier mobilities reveal that LC-1increases the FF and PCE,because of charge separation.31,32To investigate the carrier mobilities (electron and hole)in the blend films,the J −V characteristics of the hole-only (ITO/PEDOT:PSS/LC-1or PDI-1:P3HT/Au structure)and electron-only (Al/LC-1or PDI-1:P3HT/LiF/Al structure)devices were measured for the as-cast and annealed blended films (see Tables 3and 4).The hole and electron mobilities were extracted using the SCLC model 33,34(Figure 8).For the annealed blended film at 120°C,the values of the hole and electron mobilities are ∼1.07×10−6and ∼1.28×10−5cm 2/(V s),respectively.However,the hole and electron mobilities fortheFigure 6.AFM height images (5μm ×5μm)of blended thin films of P3HT:LC-1before thermal annealing (A)at 25°C,P3HT:LC-1=1:1;(B)at 120°C,P3HT:LC-1=1:1;(C)at 25°C,P3HT:LC-1=1:2)and after thermal annealing ((D)at 120°C,P3HT:LC-1=1:2;and (E)at 120°C,P3HT:PDI-1=1:1).Figure 7.Current density versus voltage (J −V )characteristics of anelectron-only device based on (●)LC-1at 25°C,(○)LC-1at 120°C,(■)LC-1at 165°C,and (□)PDI-1at 120°C at an electric field strength of 0.3MV/cm.Table 2.Performance of the Single Electron Devices LC-1with Di fferent Thermal Annealing Conditions fromChloroform Solution Used for Spin Coating at an Electric Field of 0.3MV/cmtemperature [°C]μ[cm 2/(V s)]μ0[cm 2/(V s)]γ[cm/V]LC-125 4.90×10−61.16×10−70.006850 1.72×10−57.81×10−60.0014802.91×10−5 1.05×10−50.00181003.92×10−5 1.02×10−60.0066120 2.85×10−4 1.92×10−50.0049150 2.93×10−5 3.95×10−70.0078165 1.74×10−55.37×10−60.0021PDI-1a1205.83×10−5 4.35×10−70.0089aThe single electron device based on PDI-1from chloroform solution used for spin coating at an electric field of 0.3MV/cm.as-cast blend are ∼1.07×10‑7and 8.20×10−8cm 2/(V s),respectively.As the annealing temperature increases up to 120°C,the hole mobility and electron mobility increase,which can be attributed to the improvement of film morphology and,thereby,is the reason for the higher PCE.However,the hole mobility and electron mobility of the PDI-1:P3HT film are 5.52×10−5and 4.58×10−7cm 2/(V s)at 120°C,respectively.Obviously,the strong aggregation tendency of nonliquid crystalline PDI-1can result in more charge recombination and unbalanced charge transport in the blend films,which explains the lower performance of PDI-1:P3HT BHJ devices.Since the investigations of all of the above devices had indicated that the annealing temperature played a decisive role in improving the PCE,mobility,and morphology,thoroughly investigating the thermal properties of LC-1should be carried out to provide deeper insight into the correlation between the liquid crystalline phase and the suitable annealing temperature.2.5.Di fferential Scanning Calorimetry (DSC),Polar-ization Optical Microscopy (POM),and X-ray Di ffraction (XRD).As shown in Figure 9,the DSC heating curve of LC-1showed two reversible transitions:at 54°C and 172°C.The corresponding transitions upon cooling were observed at 158°C and 41°C.Such information indicated a broad liquid crystalline phase (∼112°C),which was conductive to optimizing the annealed temperature for organic photovoltaic devices.The P3HT:LC-1BHJ devices that underwent annealing at 120°C generated a highest PCE,possibly because this annealing temperature was in the upper section of the liquid crystalline phase.POM (see Figure 10)experiments upon cooling from the isotropic melt gave evidence for a highly ordered mesophase which is a typical characteristics for the liquid crystalline materials.22,35−37Figure 10A at 120°C showed that the entire glass substrate covered a very compact and uniform film composed of small snow flake-like textures,in contrast to Figure 10B at 165°C with the larger and inhomogenous islets.The results implied that thermal annealing at di fferent temperature would in fluence the particle size and uniformity in the mesophases to di fferent extents and,thus,a ffect the electron mobility 38and PCE.So,there was no wonder that annealing atTable 3.Electron Mobilities of LC-1:P3HT with Di fferent Thermal Annealing Condition and the Blended Film of 2:1from o -Dichlorobenzene Solution Used for Spin Coating at an Electric Field of 0.3MV/cmtemperature [°C]μe [cm 2/(V s)]μ0[cm 2/(V s)]γ[cm/V]LC-1:P3HT 258.20×10−87.76×10‑90.004350 2.33×10−6 1.24×10−70.005380 3.33×10−6 1.36×10−70.00581009.42×10−6 4.43×10−70.0056120 1.28×10−5 1.44×10−60.0040150 3.34×10−6 3.10×10−80.0085165 1.96×10−72.33×10−80.0081PDI-1:P3HT a 1204.58×10−73.89×10−90.0087aThe electron mobility based on PDI-1:P3HT blended film from o -dichlorobenzene solution used for spin coating at an electric field of 0.3MV/cm.Table 4.Hole Mobilities of LC-1:P3HT with Di fferent Thermal Annealing Condition and the Blended Film of 2:1from o -Dichlorobenzene Solution Used for Spin Coating at an Electric Field of 0.3MV/cmtemperature [°C]μh [cm 2/(V s)]μ0[cm 2/(V s)]γ[cm/V]LC-1:P3HT 25 1.07×10−79.32×10−90.004450 2.70×10−7 4.02×10−80.003580 3.97×10−7 4.94×10−80.00391009.12×10−7 4.85×10−70.0011120 1.07×10−6 2.21×10−70.0029150 5.83×10−7 2.49×10−80.0057165 3.20×10−75.08×10−80.0033PDI-1:P3HT a 1205.52×10−52.18×10−70.0101aThe hole-only mobility based on PDI-1:P3HT blended film from o -dichlorobenzene solution used for spin coating at an electric field of 0.3MV/cm.Figure 8.Current density versus voltage (J −V )characteristics of (A)electron-only devices and (B)hole-only devices based on (◇)LC-1:P3HT at 25°C,(■)LC-1:P3HT at 120°C,(□)LC-1:P3HT at 165°C,and (◆)PDI-1at an electric field strength of 0.3MV/cm.Figure 9.Di fferential scanning calorimetry (DSC)traces of LC-1at a ramp rate of 10°C/min.120°C resulted in highest electron mobility of LC-1and the best performance in BHJ solar cells.Also,XRD experiments were in accordance with a columnar smectic ordering of the mesogens.The di ffractogram of LC-1from 25°C to 165°C are shown in Figure 11.The di ffractionpeaks of the 25°C sqample showed a relatively weak and wide single peak at 2θ=2.55°(corresponding to 34.61Å).However,upon further heating LC-1into a liquid crystalline phase,a strong and narrow di ffraction peak at 2θ=2.14°(41.23Å)and 2θ=25.85°(3.44Å)appeared and became more and more sharp as the temperature increased.The re flection at 25.85°in the wide-angle regime depicts a moderate intracolumnar long-range order with a π−πstacking distance of d ππ=3.44Å.LC-1crystalline at 165°C was the best and was much better than that at 25°C.Meanwhile,we found that,at higher temperature,the overall di ffraction peaks move slightly toward the direction of the small-angle di ffraction.While new di ffraction peaks at 2θ=9.2°,15.1°,and 17.8°emerged at higher temperature,the original peak with 2θ=21.1°in the 25°C di ffractogram disappeared in the wide-angle regime.These changes re flected that,in the liquid crystalline phase,LC-1has a highly ordered columnar smectic phase,which is similar to the results of Jin,who had studied a series of LC PDI derivatives containing amino-acids eater and found they have the parallel stacking forms in LC phase.XRD di ffraction patterns of the blended LC-1:P3HT (2:1)films reveal that thermal annealing is critical for the films ’crystallinity,as shown in Figure 12.The best annealing temperature is 120°C,which results in sharper and stronger peaks at 2θ= 2.43°and 4.66°than other temperatures.Although these two 2θpeaks are the distinct packing characteristics of all the perylenediimides,they do not appear in the XRD patterns of the films annealed at lowertemperatures (25,80,and 100°C).Thus,the side chains of LC-1endue this PDI derivative a reasonable self-tunability in packing behavior.While P3HT shows only very weak and broad di ffraction peaks,indicating quite disordered donor phases,the highly ordered arrangement in the blend film annealed at 120°C can only be attributed to liquid crystalline phase of LC-1.The above XRD results of the blended films are identical to that of the pure LC-1,which again con firms that thermal annealing at a higher temperature within liquid crystalline phase will produce optimum PCE in BHJ organic solar cells.3.CONCLUSIONIn summary,we have developed and characterized a liquid crystalline perylene diimide acceptor LC-1.It exhibited a liquid crystalline phase with a broad temperature range from 41°C to 158°C,which is essential for optimizing the thermal annealing to improve the morphology of organic films,charge mobility,and device e fficiency.The LC properties of LC-1have been thoroughly investigated by DSC,POM,and XRD.During device investigation,it is found that 120°C is the best temperature for thermal annealing,which results in the highest electron mobility in SCLC devices and highest PCE in BHJ solar cells.This temperature is in the upper part of the LC phase,at which LC-1forms highly ordered films with compact and uniform crystalline particles.The BHJ devices,using P3HT:LC-1(1:2)as organic photovoltaic active layer under-going thermal annealing at 120°C,shows an optimized e fficiency of 0.94%.In contrast,the devices based on PDI-1,which is a nonliquid crystalline PDI counterpart,only obtain a much lower e fficiency of 0.22%.Atomic force microscopy (AFM)images con firm that the active layers composed of P3HT:LC-1have smooth and ordered morphology.In SCLC devices fabricated via the spin-coating technique,LC-1shows the intrinsic electron mobility of 2.85×10−4cm 2/(V s),which is almost 5times that of the PDI-1value (5.83×10−5cm 2/(V s))under the same conditions for thermal annealing at 120°C.Because of the broad temperature range of the liquid crystalline phase of LC-1,thermal annealing at higher temperatures will result in mild aggregation and thus,improve the order and morphology of the LC-1:P3HT blended films,which is favorable for the balanced electron and hole transport and thereby higher PCE.However,when using nonliquid crystalline PDI-1as an acceptor,its strong aggregation results in poor exciton dissociation and charge transport of the blend films.Figure 10.Polarizing optical microscopy (POM)images of LC-1(under crossed polarizers)at (A)120°C and (B)165°C.Figure 11.X-ray di ffraction (XRD)patterns of LC-1at 25,80,100,120,150,and 165°C.Figure 12.XRD patterns of LC-1:P3HT (2:1)blended films from o -dichlorobenzene solution used for spin coating on ITO/PEDOT:PSS substrate.In addition,the blend films are measured at room temperature (RT)without annealing and after annealing at 80,100,120,150,and 165°C.Thus,LC-1is more competent than PDI-1.This concept of utilizing liquid crystalline perylene diimide is worth extending to other types of non-fullerene organic semiconductors in order to discover more e fficient alternatives to PCBM and further improve the performances of BHJ solar cells.4.EXPERIMENTAL SECTIONSynthesis of LC-1.N ,N ′-di((S)-1-carboxylethyl)-3,4:9,10-peryle-netetracarboxyldiimide and LC-1was synthesized according to procedures reported by Jin ’s group.22N ,N ′-di((S)-1-carboxylethyl)-3,4:9,10-perylenetetracarboxyldiimide (6.95g,12.99mmol)was dissolved in an aqueous solution of 5%NaHCO 3(100mL).ALIQUAT 336(9.6g,ca.20mmol)was dissolved in a 2:1(v/v)ethanol/water mixture (120mL).The two solutions were mixed and stirred at room temperature for 30min.The mixture was then extracted three times with petroleum ether (500mL),and the combined petroleum ether solution was evaporated to dryness.The residue was further dried at 75°C for 2h in a vacuum oven and then dissolved in dimethylformamide (DMF)(100mL).1-Bromooctade-cane (9.54g,28.6mmol)was added and the mixture was stirred at room temperature for 12h.The mixture was then poured into methanol (400mL).The product was collected as an orange powder via suction filtration and washed thoroughly with methanol.After drying,the product LC-1at 75°C in a vacuum oven to constant weight,it was puri fied by column chromatography on silica gel using 4:1(v/v)CH 2Cl 2/n -hexane as the eluent.Yield:10.50g (78%).1H NMR (400MHz,CDCl 3,δ)8.58(d,2H),8.43(t,2H),5.79(m,1H),4.29−4.10(m,2H),1.82−1.54(m,5H),1.19(d,30H),0.87(t,3H);13C NMR (100MHz,CDCl 3,δ)170.44,162.73,134.69,131.76,129.47,126.38,123.22,65.89,49.77,32.10,29.86,29.71,29.54,29.38,28.66,26.10,22.87,14.98,14.30;HRMS (MALDI-TOF,m/z):[M +Na]+calcd for C 66H 90N 2O 8Na,1061.6595;found,1061.6569.1H and 13C NMR spectra of the final product,LC-1,are provided in the Supporting Information.Materials Characterization.1H and 13C NMR spectra were recorded using a 400MHz Bruker in CDCl 3at 293K using TMS as a reference.Accurate mass correction was measured with MALDI ToF mass spectrometer (MALDI micro MX).Thermogravimetric analysis (TGA)were carried out using a Mettler −Toledo TGA/SDTA 851e at a heating rate of 10°C min −1under nitrogen flow of 20mL min −1.Di fferential scanning calorimetry (DSC)analyses were performed on a DSC Q100(TA Instruments).DSC curves were recorded at a scanning rate of 10°C min −1under nitrogen flow.Phase transitions were also examined using a POM Nikon Diaphot 300with a Mettler FP 90temperature-controlled hot stage.X-ray di ffraction (XRD)measurements were performed on a Bruker D8Avance equipped with a Huber quartz monochromator 611with Cu K α1=1.54051Å.Film thicknesses were determined on an Alphastep 500surface pro filometer.UV-vis absorption spectra in chloroform (CHCl 3)solution were recorded in a UV-vis spectrophotometer (Model HP8453)at room temperature using a glass cuvette with a path length of 1cm.Device Preparation and Characterization.BHJ organic device preparation proceeds as follows.A 15Ωcm −2resistor of indium-doped tin oxide (ITO)substrate was purchased from Xiangcheng Science and Technology Co.,Ltd.,and then the substrates underwent a cleaned course in an ultrasonic bath with acetone,ethanol,and ultrapure water and dried for 1h under a blast dry oven.Subsequently,the glasses were cleaned in oxygen plasma treatment for 10min,and a PEDOT:PSS (Clevios P VP AI 4083,H.C.Starck)solution was then spin-coated at 2000rpm for 60s onto the cleaned ITO surface,resulting in a thickness of ∼40nm,as determined with a Dektak surface pro filometer.The PEDOT:PSS layer was annealed for 30min at 120°C in air.A solution of active layer P3HT (Rieke No.4002-E)and LC-1were simultaneously dissolved in dichlorobenzene in a weight ratio of 1:1at a concentration of 15mg mL −1and stirred for 1h at a temperature of 90°C in an oil bath.Before deposition of the active layer,the mixed solution of P3HT:LC-1was filtered through a polytetra fluoroethylene(PTFE)syringe filter (0.45μm pore size).The active layer was then spin-coated on top of the PEDOT:PSS film at 600rpm (dichlorobenzene)for 18s resulting in a film thickness of ∼96nm.Aluminum counter electrodes were evaporated through a shadow mask on top of the active layer with a thickness of ∼100nm.The films were annealed at 120°C for 30min in the vacuum state.The active area of the pixels,as de fined by the overlap of anode and cathode area,was 12mm 2.The photovoltaic performance was determined under simulated sunlight,using a commercial solar simulator (Zolix ss150solar simulator,China).Device Characterization.The external quantum e fficiency (EQE)characterization of all devices was performed in air.The light output from a xenon lamp was monochromated by a Digichrom Model 240monochromator,and the short-circuit device photocurrent was monitored by a Keithley electrometer as the monochromator was scanned.A calibrated silicon photodiode (818-UV Newport)was used as a reference in order to determine the intensity of the light incident on the device,allowing the EQE spectrum to be deduced.■ASSOCIATED CONTENT*Supporting Information 1H and 13C NMR spectra of LC-1.Thermal gravimetric analysis (TGA)of LC-1.UV-vis absorption spectra of LC-1in chloroform (CHCl 3)solution and the film.This material is available free of charge via the Internet at .■AUTHOR INFORMATIONCorresponding Authors*E-mail:xiaoyi@.*E-mail:chengchuanhui@.Author ContributionsThe manuscript was written through contributions of all authors.All authors have given approval to the final version of the manuscript.NotesThe authors declare no competing financial interest.■ACKNOWLEDGMENTSThis work was supported by National Natural Science Foundation of China (No.21174022),National Basic Research Program of China (No.2013CB733702)and Specialized Research Fund for the Doctoral Program of Higher Education (No.20110041110009).■REFERENCES(1)Li,Q.,Ed.Self-Organized Organic Semiconductors:From Materials to Device Applications ;John Wiley &Sons:Hoboken,NJ,2011.(2)Li,Q.,Ed.Liquid Crystals Beyond Displays:Chemistry,Physics,and Applications ;John Wiley &Sons:Hoboken,NJ,2012.(3)Li,L.;Kang,S.W.;Harden,J.;Sun,Q.;Zhou,X.;Dai,L.;Jakli,A.;Kumar,S.;Li,Q.Liq.Cryst.2008,35,233−239.(4)Zhou,X.;Kang,S.-W.;Kumar,S.;Li,Q.Liq.Cryst.2009,3,269−274.(5)Zhou,X.;Kang,S.-W.;Kumar,S.;Kulkarni,R.R.;Cheng,S.Z.D.;Li,Q.Chem.Mater.2008,20,3551−3553.(6)Fitzner,R.;Elschner,C.;Weil,M.;Uhrich,C.;Koerner,C.;Riede,M.;Leo,K.;Pfeiffer,M.;Reinold, E.;Mena-Osteritz, E.;Baeuerle,P.Adv.Mater.2012,24,675−680.(7)Schrader,M.;Fitzner,R.;Hein,M.;Elschner,C.;Baumeier,B.;Leo,K.;Riede,M.;Baeuerle,P.;Andrienko,D.J.Am.Chem.Soc.2012,134,6052−6056.(8)Sun,Q.;Dai,L.;Zhou,X.;Li,L.;Li,Q.Appl.Phys.Lett.2007,91,253505/1−253505/3.(9)Struijk,C.W.;Sieval,A.B.;Dakhorst,J.E.J.;van Dijk,M.;Kimkes,P.;Koehorst,R.B.M.;Donker,H.;Schaafsma,T.J.;Picken,。
偶氮基团修饰的苝酰亚胺染料的合成及其光响应行为
ｌ 实 验 部 分
１ ． １ 仪 器 与 试 剂
基 金 项 目 ：国 家 自 然 科 学 基 金 （ ５ ０ ５ ７ ３ ０ １ ９ ／ ５ １ ２ ７ ３ ０ ６ １ ） ； 教 育
第４ Ｏ卷 第 ４期
北 京 化 工 大 学 学报 （自然 科 学 版 ）
Ｊ ｏ ｕ ｒ ｎ ａ ｌ ｏ ｆ Ｂ ｅ ｉ ｊ ｉ ｎ ｇ Ｕｎ ｉ ｖ ｅ ｒ ｓ ｉ ｔ ｙ ｏ ｆ Ｃ ｈ ｅ ｍｉ ｃ ａ ｌ Ｔ ｅ ｃ ｈ ｎ ｏ ｌ ｏ ｇ ｙ（ Ｎａ ｔ ｕ ｒ ａ ｌ Ｓ ｃ ｉ ｅ ｎ ｃ ｅ ）
了巨大 的应 用前 景 ¨ 。 酰亚胺 类化 合 物 具有 大
的 一 订共 轭 电子 体系 结构 ， 是 一 类 性 能优 异 的 ｎ型 半 导体 材料 ， 已广泛 应用 于有 机 电致 发 光二极 管 、 太 阳能 电池 、 场效应 晶体 管 和 分 子 器 件 等 高新 技 术 领 域 Ｊ 。将 偶 氮生 色 团和 茈 酰亚 胺 从 不 同角 度 ， 通 过 不 同方 式 实现 两者 功 能 特 性 的 互补 、 重组 和集 成 已 引起研 究人 员 的关 注 ， 如Ｆ ｅ ｎ ｇ等 。 。 将 Ｎ一 十 二烷 基 一 茈． ３ ， ４ － 甲酸 酐－ ９ ， １ ０ 一 亚胺 与 １ ， ４ － 二 氨 基 偶 氮 苯 缩 合， 得 到一 种 Ｎ 一 十二烷基． Ｎ 一 偶 氮 基 团取 代 的不 对 称茈 酰亚 胺 化 合 物 ， 由于分 子间 强的 盯 一 盯堆 积 作
中 图 分 类 号 ：０ ６ ４ １
引 言
偶 氮苯 生 色 团 具有 一 种 特 殊 的光 响 应 性 能 ， 在 光 照激 发下 吸收 光 能会 产 生 可 逆 的顺 反 异 构 ， 且 在
苝酰亚胺类物质的研究进展
苝酰亚胺类物质的研究进展⼀：苝酰亚胺的研究进展3.1.1 ⽔溶性的苝酰亚胺类物质的研究进展从Kardos在1913年合成第⼀个苝系衍⽣物以来,⼈们开始对苝系衍⽣物的合成进⾏了多⽅⾯的探讨。
⼤多数苝酰亚胺化合物以其难溶性⽽著称，对于如何提⾼苝⼆酰胺的溶解性，⼀直是研究的热点之⼀。
对于如何提⾼苝⼆酰胺的溶解性研究者们⼀般采取两种⽅式解决，其⼀是Langhals教授提出，在酰亚胺的氮原⼦上引⼊增溶性的基团，这样得到的分⼦在吸收和发射特征上没有明显的分别，这是由于酰亚胺基团的氮原⼦上产⽣的HOMO 和LUMO轨道的节点（node）减弱了苝核同与氮相连的取代基的耦合作⽤。
其⼆就是BASF公司的Seybold教授⾸次提出的在海湾处（bay-area）引⼊取代基，即在苝四羧酸⼆酐和苝四羧酸⼆酰亚胺的1,7或1,6,7,12位上引⼊增溶性取代基团。
2003年，D.Y.Yan等⼈将低聚的分⼦与苝核连接在⼀起，得到了溶解性良好的关于苝系的聚合物。
2006年，H.Tian等⼈⼜将与苝相连的聚合物链的长度加长，得到了溶解性更好，光电性质良好的苝系衍⽣物进⽽可以应⽤于太阳能电池领域。
2008年Y.J.Shen等⼈⼜将含硫原⼦的杂环长链接在了酰亚胺的位置，同样得到了溶解性、电化学性质都良好的有机多功能分⼦。
2009年，S.Icli等⼈⼜将上述苝系衍⽣物的燕尾形的扩展为⽤氮连接的长的脂肪链，同样的增加了苝系衍⽣物的溶解性，并研究了它们的光物理性质和电化学性质，进⼀步扩⼤了苝系衍⽣物的数量。
2007年P.A.Troshin等⼈将苝酐⽔解变成羧酸盐进⽽变为酯，同样可以改善此类化合物的溶解性，这种化合物的光物理性质和电化学性质使其成为有机光转换材料。
2009年H.Z.Chen等⼈⼜将苝酐的⼀侧做成酰亚胺的形式，另⼀侧⽔解成酯的形式，同样使得化合物具有良好溶解性。
⼆：苝酰亚胺类物质的应⽤难点、热点以及前景举例3.2.1苝酰亚胺类物质的研究热点苝酰亚胺类化合物作为⼀类有机功能性染料,由于具有化学、热和光稳定性较好,吸收光谱范围较宽以及荧光量⼦产率较⾼的特点,除了在传统的染(颜)料⾏业中继续发挥作⽤外,还被⼴泛应⽤于有机光导材料、有机电致发光材料、液晶显⽰材料、激光染料、化学发光⾊素、染料敏化太阳能电池和分⼦开关等领域。
新型苝酰亚胺衍生物的合成及其光学性能
结构经 Ｍ Ｈ Ｎ Ｒ和 Ｍ Ｓ表征 。用 ｕ －ｉ和荧光光谱研究 了他们 的光学性质 。 ＶＶｓ 关 键 词 ： 四酸二酐 ； 茈 菲酰亚胺 ； 合成 ； 光学性质
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Ｊ ． ｚ ４ Ａ Ｈ） ７ ２ （ ， ＝８４Ｈ ， Ｈ， ｒ ，． １ ｄ Ｊ＝８４ ｚ ８ ．Ｈ ， Ｈ， ＡＨ） ６ ８ （ ， ８４Ｈ ， Ｈ， ｒ ， ．０ ｓ ｒ ， ．７ ｄ Ｊ＝ ． ｚ ８ ＡＨ） ３５ （ ， ２ Ｈ，Ｏ ，１ ２ ｓ ６ Ｈ） ． ６（ ，３ Ｈ，Ｃ ） Ｈ３ ；ＭＳ（ Ｌ Ｉ ＭＡ Ｄ —
（ ｅｅｒｈＩｓｔｔ ｏ ｈ ｍｃｌ ｅ ｎｅ Ｂ ｉｎ ０ ２ ５ Ｃ ｉａ Ｒ ｓａｃ ｔｕ ｆ ｅ ｉ ｆ ｓ ， ｅ ｉｇ１２ ０ ， ｈｎ ） ｎｉ ｅ Ｃ ａＤ ｅ ｊ
Ａ ｓ ａｔ Ｔ ｒ ｏｅ ｐｒ ｅｅｄ ｍｄ ｅｖｔ ｅ， Ⅳ 一ｉ １ ｅｔｈｘ１一ｅ ｌ ｅ ， ， ，０ ｂｔ ｃ： ｈ ｅ ｖｌ ｅ ｌ ｉ ｉ ｄｒ ａｖｓ Ｎ， （ 一 ｎ ｌ ｙ） ｒ ｅ － ４ ９ １一 ｒ ｅｎ ｙｎ ｉ ｅ ｉ ｉ ｄ ｐ ｙｅ ｐ ｙｎ ３
标 ） Ｂｕｅ ａｏｉ ｌａｌＸⅡ ＭＡ Ｄ －Ｏ ／ ； ｒｋｒＤ ｈｎｃ Ｕｔ Ｆｅ ｓ ｒ Ｌ Ｉ Ｆ Ｔ
ＴＦ Ｏ 型质谱仪。 ９ ．０ ｛ Ｍ＋ ］ 。 ｌ 一 戊基 己胺 － ， ．４氨基 苯基 ） 氟 异 丙 ６９ ５ １ ［ Ｈ ｝ ９ ２（ 一 ］ 六 用３ 替代 １ 用类 似的方法合成 Ⅳ， （ 一 ， Ⅳ一 １ 二 醇 ｍ 和四氯茈酐（ ） ¨ ３ ¨ 按文献方法 自制 ；， １含量 戊基己基）１６７ １一 －， ，， 四氯－，， ， 四羧酸二 ２ ３４ ９ １ ０ ９ ％， ｈ ｅａ； － ８ Ａ Ａ ｓ Ｎ 甲基吡咯烷酮（ Ｍ ） 含量 ｒ Ｎ Ｐ，